DE1644306A1 - Process for the production of dyes - Google Patents

Description

PATENT LAWYERS DR.-ING. WOLFRAM BUNTE

D 8 MUNICH 15, HAYDNSTRASSE 5. FERNRUF CO8I1) 534712

Munich, January 10, 1967 M / 8515

Ferfahren for the production of dyes

The invention relates to a process for the preparation of new dyes of the general formula

A-NR- (° ^H ₂ ) _n - ¹ ^ 'i ¹ )

in which R and R * are identical or different and are hydrogen, a lower alkyl or a lower hydroxyalkyl radical and η is an integer from 2 to 6 inclusive «Da · symbol A can

a) represent an unsubstituted anthraquinone radical, in

009851/1930

which palle is the chain NR- (CHg) _n ^{-NHR 1} in the 2-position and R and R * denote hydrogen,. T?) An anthraquinone radical of the formula

(II)

oein, whereby in this case R always denotes hydrogen and Z ¹ denotes hydrogen or the group NHR ₁ , in which R ₁ denotes hydrogen, a niedereθ alkyl radical, and Z denotes hydrogen or the group NRR ", in which R denotes the above an- '-' has given meaning and R "can be hydrogen or a lower alkyl group or the group - (GHg) ₁₁ -NHR ¹ , in which R * and η have the meanings given above. As far as the substituents Z and Z ^{1 of} the anthraquinone nucleus are concerned, the following should be noted:

1. When calibrating the chain -NR- (CHG) _n -NHR given in formula (I) * befin- on Anthraohinonkern 1 in abutment condition. · Det, DAS so symbol can Z ¹ is hydrogen and the symbol Z, it does not Unless Hydrogen means »only take positions 4, 5 and 8.

2. If old mentioned, contained in formula (X). Chain is in the 2 position, so and BS S and Z * Was-

0 (f9 8 5 v1 / 19 * 30 *

16U306

aeratoff. *.

3. When calibrating the chain contained in formula (I) in 5-

Position is, 'then R ¹ denotes hydrogen, Z ^{1 is} a group -NHR ₁ in the 4-position and Z is the group -HKH ₂ An 1-position, where R _{2 is} hydrogen or a lower alkyl radical and R ₁ and R _{2 are the} same or can be different.

The symbol A can also '

c) an anthraohinone radical of the formula

(V)

represent, in which Ri and R £ can be identical or different and denote hydrogen, a lower alkyl radical, the chain corresponding to formula (I). . HR- (CH ₂ ) ^ - HHR ¹ on the anthraquinone nucleus can be exclusively in the 5-position and R and R * therefore always mean hydrogen}
d) a Vorael azo radical

B ₁ -HHB ₂ ■■ - ■■ (Ht)

00985ι, 1/1930

be, in which B 1 and B ₂ each represent an aromatic or heterocyclic radical which can be substituted one or more times by halogen, nitro, alkyl, hydroxy or amino acyl groups; θ), a p-nitrophenyl-azo-phenyl radical of the formula

(VI)

in which the chain -27R- (CHg) _n -NHR ¹ contained in formula (i) is in the 4-position and the NO ₂ group in the 4'-position.

Finally, the symbol A can too f) a fhenyl group of the formula

OR "·

(IV).

I-

mean, in which R ¹ "represents hydrogen or a lower alkyl radical, the chain -NH- (CH ₂ ) in which R is hydrogen and R ^{1 has} the meanings given above, in the para position eur alkoxy group is · ·. ~ : \. Well the process according to the invention are dyes

00985.1 / 19'3ΰ

of the formula (I) ₁ in which A is a radical of the formula (XX) which has a chain M- (CKg) _n -IiKR 'in the! -position, Manufactured in such a way that a diamine is the formal

cC- or KH ₂ - (CH ₂ J _n -NHR ¹ with ei no / Mono 7 !, 5- to 1. 8 ~ Dihal © genanthraohinar or is also condensed with quinizarin "

• ■ ·

This process can also be carried out in such a way that aur the production of dyes of the Ρονήβΐ (X) »'in which A means a radical of the Porrael (XI), w © loh® @ iaa 2-St © llung a chain UH- ( CH ₂ ) _a -HH ₂ , the 2-amino aatlrachinon ■ aunäohet with an aryl sulfo chloride t ^ set iiad the alkali compound of the thus obtained 2-Alain © -aryleulf @ E2rl ~ amthraohinons with a 60 , W-dihaloalkane for Ileafctlon gebi'acr.-; whereupon the halogen βΠν & τ obtained thereby with

and

condensed, v * o4> o4fAicwx? oae « ⁽ after the condensation, the arylsulfonyl radicals are split off and so the result is

Sulfuric acid and with

held fhthaliaidoderivat with, / HydrüaiDiiydrab hyörülegiert will"

Welters can do the nvt indusgsg @ muss @ Verfsiirtm mm @ h. To be carried out in such a way that daoe sur He ^ stellii »^ ¥ @ n fa ^ materials dor formula (I) _t in dene» A a radical aer J? On?,; 2. (££) means »

I ¹

because in the 5-position there is a chain HH- (OH ^) _n -HUg. l, 4 ~ diamino-5-nitro-anthraohinone with a diamine which is fom @ l condensed · ■ '/

Vemer can use dyes with the formula Cl) »in ^ © 3> ®! Μ» ε Α

009851/19 * 3

is a radical of formula (III), obtained by coupling the diazonium salt of an amine of formula B ₁ -NH ₂ with an amine of formula B ₂ -NR- (OH ₂ ) J ₁ -IIHR ¹ , where B ₁ and B ₂ represent aromatic and / or heterocyclic radicals which can optionally be substituted one or more times by halogens, nitro, alkyl, hydroxy or aminoalkyl groups.

Me dyes of the formula (I), in welohen A is a radical of formula (IV) are, in the ^r V. else made that in the Aninogruppe of amines of the general formula · -

OR »

(VII)

the group - (OHg) _n -KHR ^{1 is} introduced.

new

The compound of formula according to which I possess corresponding dyes & tadaiigsgea & Beeb method erhältIiohea _s zahlreiohe

i--

Advantages. They show 2, B * a great affinity for Keracv fibers and the dyeings carried out with them are very resistant to the waeohon of the fibers. In addition, these dyes can be used to achieve a very wide range of huanoes, ranging from oil to blue, and of very long-lasting colorations . . ■ *

009851/1330 "

16U306

'Veiter show the dyes also the advantage that they are within are soluble in water over a wide pH range «

The following exemplary embodiments serve for the better Understanding of the subject matter of the invention without being in any way limiting.

009851/1930

EXAMPLE II Preparation of 4-methylamino-1- / 3-aniinoethyl) -amino7 «-6nthraquinone .

The reaction proceeds according to the following scheme:

O '" NHOH ₂ -CH ₂ -NH ₂

NH ₂ - (OHg) ₂ -HH ₂

NH-CH,

A solution of 4-methylamino-1-brbm-anthraquinone in toluene is refluxed for several hours in the presence of an excess of ethylenediamine. After cooling, the solution containing toluene is treated several times with n-HCl. The hydrochloric acid extracts are combined and made alkaline to liberate the base, which is extracted with ethyl acetate. After adding oxalic acid to ethyl acetate solution, the desired ale oxalate precipitates and is separated off. The corresponding base is obtained therefrom in the usual way by means of alkali; they eohmilßt, NaOH recrystallization from toluene at 163 ⁰ C.

The 4-methylamino-l- / Tß-aoe1; Q ^T ainoethyl) -> aminp7 ~ anthraohinone is prepared from this base by adding casigo acid anhydride to a solution of 4-methylemino-l- / Tü-aminoethyl) -amino7-anthraohinone lh ethyl acetate added · The mono-acetate sohmelt after recrystallizing aue n-eropyl alcohol at 220 ⁰ O.

009851/193 0 '

BATH ORIGINAL

analysis regretted 9 ^N 3 for a 67 found ^C 19 ^H 1 , 65 ° 3 5 C 5ft 67 , 64 12th , 50.- II $ δ 5 , 46 .86 N f » 12th .20 - - 67.44 • 5.84 • 12.22

Example 2: Preparation of 4-methylamino-1

■ 4

/ X Äf-aminopropyl) -amingZ-anthraöhinon The reaction proceeds according to the following scheme:

KHCH,

A solution of 4-methylamino-1-bromo-anthracite in a solvent such as toluene is refluxed for several hours in the presence of an excess of 1,3-diaminopropane. After treatment of the reaction mixture, analogously to Example 1, the 4-Methylaiaino-l- ^ y <-aminopropyl) -amino7-. anthraohinone obtained, which afterwards recrystallization from toluene feel 142 ⁰ O. *

For this connection, a molecular weight of 309 is calculated; experimentally, the potentiomatic analyte dtr value 303 is determined for this. '-

00985] / 1930 '

BATH ORIGINAL

16-306

The monoacetate produced from this base melts

at 224 ⁰ O.

Example 3 Preparation of 1- / C | K-aminopropyl) -amino7-anthraquinone

The reaction proceeds according to the following scheme:

O Cl O HH- (CH ₂ ) ₅ -HH ₂

H ₂ K- (OH ₂ J ₃ -

A solution of 1-chloro-anthraquinone in a solvent such as toluene is heated under reflux cooling for several hours in the presence of an excess of 1,3-diaminopropane. After cooling, the toluene solution is treated several times with n-HCl solution. The salt acid extracts are combined and made alkaline in order to set the base free. This base crystallizes out and is separated off; after recrystallization from toluene it melts at 152 ⁰ O.

I—

From this base the l- / n ^ -Aoetaminopropyl) -amine [3] annthraohinone is prepared, in which a solution of 1- / [1] - aminopropyl) -aminopropyl) -amine7-anthraquinone in ethyl acetate is given to beige acid anhydride. This monoacetate eohmilat naoh krietaiieieren from ethyl alcohol at 202 ° 0.

00985Ü / 1930

~ 11

16U306

jj AnaljToe "calculated for 70 found 70.70 C $> 70.81 5 .73 - 5.62 Η "# 5.59 ' 8th .61 - 8.45 N # ■ 8.69. .54 -

With S ₁ Ji ie 1 4: Production of 1- ^ Cß-Aminoutthyl) - aminp7-2-nitro- »4- * nethoxy-benaol '...

The reaction proceeds according to the following topic:

0 CH,

KO ₂ Cl

HH,

0 CH

NHSO

0 GH

Br CH ₂ CH ₂ Br

OCH ₃

NO,

SO ₄ H ₂

N-OH ₂ -CH ₂ Br

009851/1930

16U306

NO ₂ potassium uraphthalimide ■

HH OH ₂ CH ₂ Br

Hydrazine hydrate

NH-CH ₂ OH ₂ SH ₂

The individual phases of this synthesis are described in more detail below _: ΑΛ
1 «Phases production of! *> (P-toluene-eulfonyl-aminoy-2-nitro-,

4-methoxy-benzene

To an oinor solution of 0.1 mol (16.8 g) of l-amino-2-nitro-4-iaothoxybenr.ol in 60 om ^ pyridene, 0.12 mol (22.86 g) p-Toluoloulfochlorid zugesetf.C After completion Zua & tz, the reaction mixture is kept at room temperature for 6 hours and then 300 g of bis daa ⁵ hydrochloric acid is treated with 30 cm cast. The separated crude product is redissolved in n / 2 NaOH solution and the alkaline solution is filtered, 4 g of the starting product insoluble in HaOH being recovered . After neutralizing the Piltratep with hydrochloric acid, 25 β! PHP-toluene-sulfonyl-amine 2-nitro-4-methoxy-boneol are obtained, which according to Uaücriet are aiii

009851/193 0 *

SAD

from alcohol at 102 ⁰ O sohmilat.

analysis calculated for ■ found . 52.28 ^C 14 ^H 14 ° 5 ^! * 2 ^p 4.44 O # 52.17 52 , 09 - 8.92 H # 4.34 4th .43 - H $ 8.69 8th .74 -

2nd phase: production of the sodium compounds a 1 ^ (p-toluene- '.' 8ulfonyl ~ amlixo) | 72-iii ^< bro-4- »ie1; h03iy-beni2olQ

A solution of 0.155 mole of p-^ Toiuo! -Qiilfor ^ l ~ ~ amino3J 2-jiitro-4-methoxy-benzene in 600 om 'n / 2 liaOH are added with stirring 250 enter? 1On-HaOH is added, 48 g of the sodium compound being obtained, which mil; little alcohol and therefore can be washed with a little ace bon *

3rd phase production of l- / ii- (p «! L ¹ oluolaulfoii _b jrl) -lI» (ß-broDi-

ät & yl) -amlno7-2-ni tro-4-itte thoxy «benzUl

0.0103 Hol (3.56 g) of the lithium compound of L- (p-toluene-BUlfonyl-amino) -2-nitro-4-ynethoxyben2iol will be in 5 ^

Dimethylformamide lust "0.023 mol (2 cm ^p ) 1,2-dibromothane are added to this solution the suction with n / 2-NaOH is used to remove small amounts of .ΐΛ ρ-toluene-sulfonylamino) -2-nitro-4-mefcho3cy-benßOl outside) then with

009 8 5J / 1 9 * 3 Cf

BATH ORIGINAL

Washed water, the liquid concentrated to about -10 cm and mixed with a little hexane. 2.7 g of l-ZN-Cpsulfonyl) -N- (ß-bromoethyl) -amino7-2-nltro-4-methoxy-benzene were obtained, which after recrystallization aue abs. Alcohol at 117 ⁰ O melts.

analysis calculated for "
3 Br 44 found 44.94 ο 56 44.75 4th .79 - 4.14 η i » 3.96 6th .17 - 6.61 H # 6.52 .73 -

4 · Phase ί Production of 1- ^ Sf- (ß »Broraäthyl) -ainino7-2-nitro-» Φ 4-methoxy-benzene

0.095 mol (40 g) l - ^ - ip-foluene-flulfonyD-N-iß-bromoethyl) -aittino7-2-nitro-4-mefcho3cy-bonzol are dissolved in 160% concentrated egg acid, whereby the temperature increases 0 - 5 ⁰ C is maintained. The Reaktlonsmiachung is allowed to stand for 3 hours and then poured onto 1.2 kg gestOBsenes Kia at 0 °, üb

25.1 g ! - $ - ( fl-bromoethyl) -amlno7-2-ttitro-4-mefehoxybenzene are obtained, daa na oh Uakri at alIisiθγθη from a Beneol- / Hsxan-RlsohuQg at 37 ⁰ o sohmilat.

164A306

analysis calculated for
O ₉ H ₁₁ N ₂ O ₃ Br found G? 6
H #
H 1> 39.27
4.00
10.18 · 39.41-39.36
4.18-4.20
10.39-10.27

5th phase Production of l- / egg- (ß-phthalimidoethyl) -ainino7-2-nitro - ^ - methoxy-benaol

0.27 mole (74 g) of l - ^ - (β ~ bromoethyl) «aiaino7-2-nitro-4-methoxybenzene are dissolved in 290 cm of dimethylformamide. This solution contains 0.32 mol (59.5 ß) ksiliumphthalimid sugesetst. The mixture is heated for one hour on the Huok flow cooler, then it is filtered at the boil. Flat AIJIcUhIuIi ₀ % Piltratß are 79 δ, Λ lZ? - (ß-Phthalimidoäthyl) -> aminjg7-2 ~ nitro-4-methoxy-benzene, which melts ^{at 212 0 O after recrystallization from dioxane.}

analysis calculated 5 ^H 3 for 59 found . - 59 , 73 ° 17 ^H 1 , 82 ° 5 4th .- 4 , 60 0% 59 , 39 12th , 61 - 12 , 48 H 5t 4th , 31 , 42 12th , 50

6th phase: Production of l - ^ - (ß-AminoäthyD-amino7-2-nitro 4-methoxy-bennOl -

009853/19 ^ 3

BAD DRlGlNAt

A solution of 0.1 mol (34.1 g) l - ^ - (ß-Bhthalimidoäthyl) -amine £ 7-2-nitro-4-methosy-benzene in 350 cm 'of propanol together with 0.2 mol (10.2 g) of hydrazine hydrate is added for one hour heated under reflux for a long time. The cohesive mix is filtered to separate the phthalhydrazide formed; after cooling the filtrate, a small amount will not converted initial product recovered by filtering it off. The propanol solution is then mixed with gaseous hydrogen chloride saturated, with 22.5 g of the desired product as the chlorohydrate obtained, which is urakristaiized from water

analysis calculated for , 63 43 found C # 43 , 65 5 .79 - H* 5 , 96 17th .65 H# 16 . 05 - • 43.80 • 5.70 - 17.08

The l- / R- (ß-aminoethyl) -araino7-2-nitro-4-methoxy-benzoil isolated from this hydrochloric acid in the usual journey melts at 57 ° 0

Example -5 »Preparation of 1,4-diamino-5- ^ jK ^ aminopropyl ) -amine ^ -anthraohinone

The reaction proceeds according to the following topic:

009 8 5 3/1930

Ö NH,

HH ₂ -

NO ₂ O NH ₂

0.4 Molji (113.2 g) l ^ -Diajaino-S-nltro-anthraquinone are heated in 6 mol (4 * 44 g) 1,3-diaminopropane to 90 ⁰ O for 4 hours. The reaction mixture is poured into 2 liters of cold water; 109 g of crude product are obtained, which is very carefully grown with vaseer.

After recrystallizing twice from Eropanol, ' φ

72 gi, 4-i) iäinino-b-2f j ^ -aJidhöprbpyi) -aiRin £ ^ -äriini? Äoiiihon, which melts ^{at 165 0 C.}

analysis calculated for
° 17 ^H 18 ° 2 ^H 4 found O #
H*
H? 6 65.80
5.80
18.03 65.8? ..- 65.61
5.95-6, Q3
17.78-17.90

Example 6 t Preparation of the Aao Compound

0.2 mol (27.6 g) of p-nitroaniline are dissolved in ealneaurem Hilieu

diaaoted in the usual way. 8UR hydrochloric solution of the resulting! UiazöniumBalzes a solution of 0.2 mol (32.8 g) N- (ethyl) -K- (beta-aminoethyl) aniline in 30 cm ⁵ Easigsäure added dropwise at about 5 ⁰ O. Here will be
72 g of the azo compound were obtained as a monohydrate.

This hydrochloride is dissolved in boiling water and the solution made alkaline, leaving 56.58 g of the azo compound obtained after recrystallization from alcohol and

■■ *, -

then melts from benzene at 134 C.

analysis calculated for
C ₁₆ H ₁₉ N ₅ O ₂ found O $>
H yo 61.34
6.07
22.36 61.35-61.30
6.14-6.20
22.44-22.29

Example 7: Preparation of 2- / Tβ-aminoethyl) amine £ 7-anthraquinone

The reaction proceeds according to the following scheme:

O ₆ H ₅ SO ₂ oil

BH SO ₂ O ₆ H ₅

0 098 5 M 19äo '

BATH ORIGINAL

1 6AA306

KOH,

BrCH ₂ -OH ₂ Br ^?

, 0H ₂ -CH ₂ Br

SO ₂ O ₆ H ₅ /

SO ₄ H ₂

NH-CH ₂ -OH ₂ -H 0

NH-CH ₂ -CH ₂ NH ₂

Hydrazine hydrate

1. Phases Heistelluiig of 2 - ^ - (Benaoleülfoiiyl) -aniiyi7-onthraohinon

009853/1 9Ϊ3Ο

To a solution of 1 ha (223 g) of 2-amino-anthraohinone in 1800 on ⁵ pyridine, 1.32 ha (166 on?) Of bensole sulfochloride are gradually added ^{at 45 0 with stirring.} Naoh this addition the Reaktionamischung is kept for 4 hours at 45 ⁰ O and then cooled to 0 °. The crude product separated off by filtration is washed first with water, which has been slightly acidified using hydrochloric acid, then with water and finally with alcohol. There are thus obtained 320 g of virtually pure benzene sulfonamide, the sohmilzt at 276 ⁰ C · From the Pyridinfiltrat can be obtained by diluting 12 g Nooh slightly less pure Benzölsulfonamld. 2nd phase «production of 2 - ^ - benzenesulfonyl-N- (ß-bromoethyl) -

amino7-anthraohinone

0.05 Hol (18.15 g) 2 ~ / F-Benzol8ul £ onyl-uuin ^ -anthraquinone are dissolved in 90 cm ^{5 dimethylformamide at 6O 0 O.} A solution of 3.08 g of KOH in 2 cm 'of water and 6 oar of alcohol is added to this solution, and then 0.1 hol (18.8 g) of 1,2-dibromoethane is added as quickly as possible. The reaction mixture is left to stand for 2 hours in a cooing water bath and then poured into 1 l of ice water. The separated crude product is treated with n / 2-HaOH in order to remove small amounts of unreacted 2 - ^ - benzenesulfonyl-aminoj-anthraohinone and then washed with water. 15 g of 2- ^ ~ Benaoleulfonyl-N- (ß-bromoethyl) -amino7-anthraohinone are obtained, which melts at 155 ⁰ O after recrystallization from liquid acid.

0098551/1930

3rd phase; Production of 2 - ^ - Bensolsulfonyl-N- (ß-pJrfchalimidoäthyl) -amino ^ -anthraquinone

0.317 mol (14.6 g) 2- ^ f-benzenesulphonyl-N- (ß-bromoethyl) -araino7-anechhraquinone are dissolved in 675 cm dimethylformamide. 0.412 moles (76.5 g) of potassium sulfide are added to this solution. Di © reactions! Echung is heated one hour under © HückfluBekühlung since cooled and poured into 6 '1 "liiswasaer." Ba will get 138 * g of crude product which iiaoh i% teiatalliaieren of acetic boi 236 ⁰ C echmilsst.

analysis calculated for 67 found 66.83 ^C 30 ^H 20 ^N 2 O ₆ S 3 3.80 C 1 » 67.16 5 , 07 - 5.20 H $> 3.73 .87 - N # 5.22 .27 -

4. Phaae: making 2 - ^ - (ß-

anthraohinon 0.225 mol (121 g) 2- ^ fi amino7-anthraohinon are in 600 oar

sulfuric acid

maintaining the temperature at 25 - 3O kept ⁰ O

the

EeaktionemiBohung is left for 5 hours at RnuKtümp ^ a-fcur and then on 5 legs gestoseenee Until poured "Be 87 β 2 - /? - (0-fhthalinidoethyl)" £ ^ i ^ d7-contain? Auhinoii vrliülten, the at 270 ⁰ O iohnilat. '

00985 «/ 1950

~ 22 -

5th phase: production of 2 - ^ - (ß ~ arainoethyl) -amino7 "anthrachlnon

0.21 mol (85 g) 2- ^ 5? - (β-phthalimidoethyl) -amino7-anthraohinone dissolved in 300 cnr diethylene glycol and treated with 0.42 mol (21.5 g) hydrazine hydrate (98% lg). The reaction mixture is ^{heated to HO 0} O for 2 hours, then, after cooling, poured into 1500 cm of water, then acidified with concentrated hydrochloric acid while stirring and on a boiling water bath

• ι

Heated to dissolve the chlorohydrate formed, and after cooling, 59 g of 2 ~ ^ / ¥ - (ß-Aminoethyl) -aminoJ7-anthracemonic chlorohydrate are obtained, which contains a small amount of thalohydrazide chlorohydrate. Dieseo crude product is treated with 350 ca ^ 2n-K0H, whereby 45 g of practically pure 2 - obtained (öäthyl) -amino7-anthraohinon, melts the NaOH Iieieron of pyridine at 180 ⁰ C - ^.

analysis calculated for
O ₁₆ H ₁₄ H ₄ O ₂ found C #
HJi
N 56 72.18
5.26
10.52 72.43,. ^ 72.35
5.42-5.35
10.54-10.40

009851/1930

Claims (1)

Patent application Xc-htf '. Process for the preparation of new dyes of the general formula A-NR- (OHg) _n - HHR '(i) in which R ^ and R ^1, identical or different, Bind and Vaaner- ■ 4 substance, a lower alkyl or a lower hydroxyalkyl radical, η is a whole number ranging from 2 to 6 inclusive and A either an unsubstituted anthraquinone radical, in which case the chain HR- (OHg) _n -NHR ^{1 is} in the 2-position *, and R and R ^{1 are} hydrogen " " -th, or an anthraquinone radical of the formula where in this case R always denotes hydrogen and Z ¹ denotes hydrogen or the group NHR ₁ , in which R ^ denotes hydrogen, a lower alkyl radical, and Z denotes hydrogen or the group NRR ^M , in which R explains the meaning given above and R "denotes hydrogen or a low one 00 9851-1 / 1930 Alkyl group or the group - (CH ₂ ) J ₁ -NHR ¹ -, in which R ¹ and η have the meaning given above, where, eofern c6) the chain -HR- (CH ₂ ) J ₁ -NHR ¹ contained in formula (I) is in the 1-position in the anthraohinone nucleus, Z ^{1 is} hydrogen and Z, if it is not hydrogen, only positions 4, 5 and occupies 8, ß) the chain contained in formula (I) is in the 2-position in the anthraquinone ^{nucleus, R *, Z and Z 1 represent} hydrogen, p the chain contained in formula (I) is in the! »position, R * ajjs .sghj.ieealloh Wajeers / | off, Z ¹ a örü ö ^ -NM ₁ lh 4-Sieiiurig and Z Örüppö -NHR ₂ in the 1-position, where R ₂ is hydrogen or a lower alkyl radical and R ₁ and R ₂ may be the same or different, or a Anthruohinonradikal of formula ι-- 0 NHR ₉ (V) 0 NHR ^ in which Ri and R £ can be the same or different 009851/1930 and denote hydrogen or a lower alkyl radical, where the chain NR- (OHg) _n -NHR 'contained in formula (I) can only be in the 5-position of the anthraohinone nucleus and R and R * therefore always denote hydrogen, or an azo radical of the formula B ₁ -NNB ₂ (III) in which B ^ and B ₂ each represents an aromatic or heterooyolic Bchee radical which can be substituted one or more times by halogen, nitro, alkyl, hydroxy or alinoacyl groups, or a p-nitrophenyl-azo-phenyl radical of the formula N-N- / 7V-. (VI) in which the chain -NR- (GHg) _n -NHR * contained in the formula (I) is in the 4-position and the NOg group in the 4 * -S division, or ^r 'is a phenyl group of the formula (IV) 0 09851/1930 in which R "represents hydrogen or a lower alkyl radical, where the chain -NR ~ (CH ₂ ) _n -NHR ', in which R is hydrogen and R' has the meanings given above, is in the para position to the alkoxy group, could be,
characterized in that a) a diamine of the IOrmel NH ₂ - (CHg) _n -NHR ¹ with a mono- or 1,5- or 1,8-dihaloanthraohinone or with quinizarine -I is condensed, b) 2 'Amino-anthraquinone initially unsettled with an aryl sulfochloride and the alkali bond of the 2-amine arylsulfonyl-anthraquinone obtained in this way with an o & , ^ r-analogue alkane' u * reaction is obtained, WQFSUl £ & § Hälb'PnderiiJrat öit käliUttphillälimid kohdehöiöfi, ecter after the condensation dex Ary 1 sulfonyl res V abgenpaile Sulfuric acid · and with and finally the obtained phthalioido derivative with / hydra ^ in hydrate is hydrolyzed, c) 1,4-diamino-5-nitro «-anthraohinone is condensed with a diamine of the formula NH ₂ - (CHg) _n -NH ₂ , d) the D: i azoniumaolß of an amine of the formula B ₁ -NH ₂ with an amine of the formula B ₂ -NR- (CH ₂ ) _n -NHR, in which B ₁ and B _{2 represent} aromatic and / or hoterooyolishe radicals, dia can optionally be substituted one or more times by halogens, nitro, alkyl, hydroxy or aminoaoyl groups, is coupled, 009851/1930 e) into the amino group of amines of the general formula OR «« RHI (VII) the group - (CH) -NHR ^{1 is} introduced. 009851/1930 212 / Hi